Debromination of decabrominated diphenyl ether by resin-bound iron nanoparticles
Debromination of decabrominated diphenyl ether by resin-bound iron nanoparticles
复制标题
DOI：
10.1021/es070769c
复制
发表时间：
2007-10-01
影响因子：
11.4
通讯作者：
Hu, Jingtian
中科院分区：
文献类型：
--
作者：
Li, An;Tai, Chao;Hu, Jingtian
研究发现，纳米级零价铁 n-ZVI 在环境条件下且无需贵金属催化的情况下，能够非常有效地还原十溴二苯醚 (BDE209)。开发了一种将 n-ZVI 颗粒固定在阳离子交换树脂上的方法。然后将 n-ZVI 涂覆的树脂与 BDE209 在水/丙酮 (1:1) 溶液中混合，并使反应进行长达 10 天。 BDE209 消失的一级速率常数估计为 0.28 +/- 0.04 h(-1)。发现脱溴是逐步进行的，并且随着反应时间的增加产生较少溴化的同系物。还研究了十氯联苯（PCB209）的脱氯，但反应速率比BDE209的脱溴慢得多。反应产物的鉴定极具挑战性，需要通过实验和参考气相色谱相对保留时间之间的回归方程来辅助，并通过高分辨率质谱确认并参考定量结构保留关系。对于随机选择的PBDE和PCB同系物，使用量子化学计算计算单个原子的净电荷，以探索PBDE和PCB之间不同取代位置的卤素相对脆弱性的差异。 多氯联苯。
Nanoscale zerovalent iron, n-ZVI, was found to be highly effective in reductively debrominating decabromodiphenyl ether (BDE209) at ambient conditions and without the catalysis of noble metals. A method was developed to immobilize n-ZVI particles on a cation-exchange resin. The n-ZVI coated resin was then mixed with BDE209 in a water/acetone (1:1) solution, and the reaction was allowed to proceed for up to 10 days. The first-order rate constant of BDE209 disappearance was estimated to be 0.28 +/- 0.04 h(-1). The debromination was found to be stepwise, and less-brominated congeners were produced with increasing reaction time. Dechlorination of decachlorobiphenyl (PCB209) was also investigated, but the reaction rate was much slower than the debromination of BDE209. Identification of the reaction products was highly challenging and was assisted by regression equations between experimental and reference gas chromatographic relative retention times, with confirmation by high-resolution mass spectrometry and reference to quantitative structure retention relationships, For randomly selected PBDE and PCB congeners, the net charges of individual atoms were calculated using the quantum chemical computation to explore the difference in relative vulnerability of halogens at different substitution positions between PBDEs and PCBs.